Carbonic acid amides of certain substituted glyoxalidines



Patented June 21, 1949 Melvin De Groote, University City, and BernhardKeiser, Webster Groves, Mo., assignors to Petrolite Corporation, Ltd.,Wilmington, Del., a corporation of Delaware No Drawing. Application May28, 1945, Serial No. 596,398

8 Claims. (Cl. 260-309.6)

This invention relates to a new chemical product or compound, to themanufacture of said product, and to the use of said product.

One object of our invention is to provide a new chemical product,compound or material, which, in addition to being adapted for use as ademulsifier, is also capable of use for various other purposeshereinafter enumerated.

Another object of our invention is to provide a practical method ofmaking the said chemical product, compound or material.

Demulsification, as contemplated in the present application, includesthe preventive step of commingling the demulsifier with the aqueouscomponent which would or might subsequently become either phase of theemulsion, in absence 7 of such precautionary measure.

The linkage formed involves two amino nitrogen atoms connected by thedivalent carbonyl radical. It is known. however, that two moles of ureamay combine to give a mole of biuret, or, if desired, biuret itself maybe used to replace urea. Other comparable compounds, as well as biuret,may be used as the obvious equivalent of urea, for instance, thiourea,or guanidine carbonate. As to the use of such other reactants insomewhat analogous reactions, reference is made to U. S. Patent No.2,304,113, dated December 8, 1942, to Morgan et al.; and U. 8. PatentNo. 2,304,369, dated December 8, 1942, to Morgan et al.

As previously suggested, one type of raw material herein contemplated,consists of a cyclic compound having a 5-membered heterocyclic ring withtwo atoms different from carbon. More specifically, they may beconsidered as derivatives of imidazole, frequently referred to asglyoxaline. Imidazole (glyoxaline) is indicated by the followingformula:

The imidazolines or glyoxalidines may be considered asdihydro-derlvatives of (glyoxaline); and thus, the expressionsdihydroglyoxalines and glyoxalidines" are often employed. Theintroduction of two hydrogen atoms at the 4-5 position results in theconversion of imidazole into dihydroglyoxaline, which may be indicatedby the following formula:

6 2 H2 CH Fatty acid Alkylene polyamine H H'10R.C.HN.CHz.CH.R|.NH.RiXHnO Amide R-Cf 4CH: +2Hz0 1,2-disubstitutedglyoxalidine imidazole wherein R represents an alkyl or alkenyl group,such as one containing from to carbon atoms (the residue of a higherfatty acid); R1 represents hydrogen or a lower alkyl group; R2represents an alkylene group, or a lower alkyl substituted alkylenegroup and X represents a hydroxyl group, an amino group, or anaminoalkylene substituted amino group. (See U. S. Patent No. 2,214,152,dated September 10, 1940, to Wilkes. Also see U. S. Patents Nos.2,155,877 and 2,155,878, both dated April 25, 1939, to Waldmann andChwala.)

The expression higher molecular weight carboxy acids" is an expressionfrequently employed to refer to certain organic acids, particularlymonocarboxy acids, having more than six carbon atoms, and generally,less than carbon atoms. The commonest examples include thedetergentforming acids, 1. e., those acids which combine with alkaliesto produce soap or soap-like bodies. The detergent-forming acids, inturn, include naturally-occurring fatty acids, resin acids, such asabietic acid, naturally-occurring petroleum acids, such as naphthenicacids, and carboxy acids produced by the oxidation of petroleum. As willbe subsequently indicated, there are other acids which have somewhatsimilar characteristics and are derived from somewhat different sources,and are different in structure, but can be included in the broad genericterm, previously indicated.

Among sources of such acids may be mentioned straight chain and branchedchain, saturated and unsaturated, carboxylic, aliphatic, alicyclic,fatty, aromatic, hydroaromatic, and aralkyl acids, including caprylicacid, heptylic acid, caproic acid, capric acid, pimelic acid, sebacicacid, erucic acid, saturated and unsaturated higher molecular weightaliphatic acids, such as the higher fatty acids containing at leasteight carbon atoms, and including, in addition to those mentioned,melissic acid, stearic acid, oleic acid, ricinoleic acid, diricinoleicacid, triricinoleic acid, polyricinoleic acid, ricinostearolic acid,ricinoleyl lactic acid, acetylricinoleic acid, chloroacetylricindleicacid, linoleic acid, linolenic acid, lauric acid, myristic acid,undecylenic acid, palmitic acid, mixtures of any two or more of theabove mentioned acids or other acids, mixed higher fatty acids derivedfrom animal or vegetable sources, for example, lard, cocoanut oil,rapeseed oil, sesame oil, palm kernel oil, palm oil, olive oil, cornoil, cottonseed oil, sardine oil, tallow, soyabean oil, peanut oil,castor oil, seal oils, whale oil, shark oil and other fish oils, teaseedoil, partially or completely hydrogenated animal and vegetable oils,such as those mentioned; hydroxy and alphahydroxy higher carboxylic,aliphatic and fatty acids, such as hydroxystearic acid, di-

hydroxypalmitic acid, dihydroxystearic acid, dihydroxybehenic acid,alpha-hydroxy capric acid, alphahydroxystearic acid, alphahydroxypalmitic acid, alphahydroxy lauric acid, alphahydroxy myristic acid,alphahydroxy cocoanut oil mixed fatty acids, alphahydroxy margaric acid,alphahydroxy arachidic acid, and the like, fatty and similar acidsderived from various waxes, such as beeswax, spermaceti, montan wax,Japan wax, coccerin, and carnauba wax. Such acids include carnaubicacid, cerotic acid, lacceric acid, montanic acid, psyllastearic acid,etc. As suggested, one may also employ higher molecluar weightcarboxylic acids, derived by oxidation and other methods, from paraffinwax, petroleum and similar hydrocarbons; resinic and hydroaromaticacids, such as hexahydrobenzoic acid, hydrogenated naphthoic,hydrogenated carboxy-diphenyl, naphthenic, and abietic acid; aralkyl andammatic acids, such as hexahydrobenzoic acid, hydrogenated naphthoic,hydrogenated polycarboxy-diphenyl, naphthenic, and abietic acid; aralkyland aromatic acids, such as benzoic acid, Twitchell fatty acids,naphthoic acid, carboxydiphenyl, pyridine carboxylic acid,hydroxybenzoic acid, and the like.

Other suitable acids include phenylstearic acid, benzoylnonylic acid,campholic acid, fencholic acid, cetyloxybutyric acid, cetyloxyaceticacid, chlorostearic acid, etc.

Another source of suitable acids are those commonly referred to as lacacids, such, for example, as the acids derived from shellac. Such acidsinclude various polyhydroxy acids, for example, aleuritic acid, shelloicacid, and kerrolic acid.

The preferred aspect of our invention is concerned with the use ofcompounds derived from detergent-forming monocarboxy acids, whichinclude those previously described having at least 8 carbon atoms andnot more than 32 carbon atoms.

The preferred reagent in this particular case Example 11-aminoethyl-2-heptadeceny1 glyoxalidine was prepared by mixing 1 grammole (282 grams) of oleic acid, with 2 gram moles (206 grams) ofdiethylene triamine, and'heating the mixture for a period of about 16hours. under a distilling column. Water was continuously removed until atemperature of about 245 C. was reached. The quantity of water thusremoved amounted to about 1.! moles. Unreacted diethylene triamine wasdistilled from the reaction mixture under vacuum, and the residue thenwas purified by distillation at an absolute pressure of 1 mm. ofmercury, at which point it boiled within a. temperature range of 225 to250 C. About 220 grams of the 1-aminoethyl-2-heptadecyl glyoxalldine wasobtained as apale yellow liquid.

2 lb. moles of the above product are mixed with 1 lb. mole of urea andheated at a temperature within the range of C. to approximately C. until2 moles of ammonia are eliminated. This requires approximately 20minutes to 1 hour.

The product so obtained is somewhat darker in appearance, and much moreviscous than the product prior to reaction with urea. It is soluble inwater, dilute acids, etc.

Example 2 The same procedure is followed as in the preceding example,except that a different disubstituted glyoxalidine is employed, to wit,1- (aminoethyl ethylamino)-2-heptadecenyl glyoxalidine. Thisglyoxalidine was prepared by reacting 1 gram mole of oleic acid with 3gram moles (438 grams) of triethylene tetramine.

The molal ratio of glyoxalidine to urea is left unchanged.

Example 3 Tetraethylenepentamine is substituted for triethylenetetramine as a reactant in the preceding example.

Erample 4 Laurie acid is substituted as a reactant for oieic acid in thethree preceding examples.

I Example 5 Ricinoleic acid is substituted for oleic acid in Examples1-3, preceding.

Example 6 Naphthenic acid is substituted for oleic acid in Examples 1-3,preceding.

Example 7 The same procedure is followed as in Examples 2 to 6,inclusive, except the molal ratio of urea is doubled.

Example 8 Example 9 The same procedure is followed as in Examples 1 to6, inclusive, except that thiourea biuret or guanidine carbonate issubstituted for urea. Attention is directed to the fact that products ofthe kind described show unusual resistance to hydrolysis in strong acidsolution, and thus, are particularly diflerentiated from somewhatsimilar compounds in which the high molal group derived, for example,from a fatty acid is present in ester or amide form. This makes thecompounds herein contemplated particularly efl'ective for use asinhibitors in acid solution, for the formation of acid fluxes, andparticularly for use in preventing emulsions in connection with theacidification of calcareous acid structure, as contemplated in ourcopending application Serial No. 568,229, filed December 14, 1944, nowU. S. Patent 2,400,395.

It has been previously pointed out that where urea is employed in theproportion of one mole of urea for 2 of the glyoxalidine, that thestruc-' ture involves a linkage, such as the following:

NHCH:CH:NH NHCH:CH:NH

When, however, 2 moles of urea are employed for 2 moles of theglyoxalidine, a variety vof other structures may enter into thecombination, as, for example, the formation of biuret, with the resultthat there appears a linkage such as the 55 following:

cated by some of the thick, resinous products formed,that'polymerization occurs when the higher proportions of urea, or itsequivalent is 75 employed, due to the formation of a structure. asindicated in the following manner:

ii'cmcnmn I -NO BIC mm:

As far as we are aware, the reaction involving two moles of theglyoxalidine and 1 mole of the urea, involves the terminal primary aminoradicals. When additional linkages are formed, as indicated, providedthat such linkages may take place in more than 1 position, we areunaware as to the factors which determine the particular point ofreaction.

In order to properly designate the herein contemplated compounds, wehave referred to them as substituted carbamyl compounds containing atleast 2 radicals of the 1,2-disubstituted glyoxalidine wherein Itrepresents an alkyl or alkenyl group, such as one containing from 10 to20 carbon atoms (the residue of a higher fatty acid or its equivalent);R1 represents hydrogen or a lower alkyl group; R: represents an alkylenegroup or a lower alkyl substituted alkylene group; and X represents amember of the class consisting of amino groups and amino-alkylene,substituted amino groups, and having at least one occurrence of adivalent radical selected from the class consisting of:

radicals, and the aforementioned divalent radical uniting theglyoxalidine radicals by being linked to nitrogen atoms.

Compounds of the type herein described are basic in form, and it isunderstood that reference in the claims includes the free base, i. e.,the anhydro form, or the hydrated base formed by combination with wateror salts formed by combination with organic or inorganic acids, such ascitric acid, lactic acid, hydroxyacetic acid, nitric acid, hydrochloricacid, etc.

Attention is directed to U. 8. Patent No. 2,353,706, dated July 18,1944, to De Groote and Keiser. Said patent describes the oxyalkylation,and particularly, the oxyethylation of 1,2-disubstituted glyoxalidinesof the type herein contemplated as reactants. It is understood that theproducts herein contemplated may be subjected to oxyethylation under thesame conditions, and in the same manner, and in the same molal ratio asthe simpler 1,2-disubstituted glyoxalidine described in theaforementioned U. 8. Patent No.

The above product appears to form linkages which represent a particulartype of carbonic acid ester.

However, when there is one hydrogen atom attached to an amino nitrogenatom available for reaction, the following reaction appears topredominate:

In this instance the final product appears largely to conform to thatobtained by initial reaction with urea, followed by oxyethylation as asubsequent step. Oxyalkylation, particularly oxyethylation, need not belimited to 2 amino radicals, but may be employed for the modification ofa single amino radical, or for more than 2 amino radicals. There must bea hydrogen atom attached to the amino radical, i. e., the amino radicalmust be primary or secondary, in order to be susceptible tooxyalkylation.

In its broadest aspect, the present invention contemplates as such andfor various purposes, particularly including the demulsification ofcrude petroleum oil, such variants in which the imidazoline radicalcontains a group selected from the class consisting of --.\i[(R;-O),.H]zand -NH(R|--O),.H

groups, wherein R3 denotes an aliphatic radical and n is a small wholenumber greater than 2 and less than 11; or the equivalent radicalspreviously mentioned in connection with hydroxyethylene derivatives, andwhich may be indicated in a broader aspect by the following structure:

( a in' wherein R: has its previous significance and n is a small wholenumber less than 11. R: particularly represents alkylene radicals having2 to 4 carbon atoms, such as the ethylene radical, propylene radical,butylene radical. glycide radical and methyl glycide radical.

Materials of the kind herein contemplated are useful as wetting,detergent and leveling agents in the laundry, textile, and dyeingindustry; as wetting agents and detergents in the acid washing of fruit,in the acid washing of building stone and brick; as a wetting agent andspreader in the application of asphalt in road building and the like, asa constituent of soldering flux preparations; as a flotation reagent inthe flotation separation of various minerals; for flocculation andcoagulation of various aqueous suspensions containing negatively chargedparticles, such as sewage, coal washing waste water, and various tradewastes, and the like; as germicides, insecticides, emulsifiers forcosmetics, spray oils, water-repellent textile flnish, etc. These usesare by no means exhaustive as far as industrial application goes, butthe principal use of the herein described new compounds or materials, isas demulsiflers for water-in-oil emulsions, and more specifically,emulsions of water or brine in crude petroleum.

We have found that the chemical compounds herein described, which areparticularly desirable for use as demulsiflers, may also be used as abreak inducer in doctor treatment of the kind intended to sweetengasoline. (See U. 8. Patent No. 2,157,223, dated May 9, 1939, toSutton.)

Chemical compounds of the kind herein described are also of value assurface tension depressants in the acidization of calcareous oil-bearingstrata by means of strong mineral acid, such as hydrochloric acid.Similarly, some members are eifective as surface tension depressants orwetting agents in the flooding of exhausted oil-bearin strata.

As to using compounds of the kind herein described as flooding agentsfor recovering oil from subterraneanstrata, reference is made to theprocedure described in detail in U. 8. Patent No. 2,226,119, datedDecember 24, 1940, to De Groote and Keiser. As to using compounds of thekind herein described as demulsiflers, or in particular as surfacetension depressants, in combination with mineral acid or acidization ofoil-bearing strata, reference is made to U. 8. Patent No. 2,233,333,dated February 25, 1941, to De Groote and Keiser. I

A somewhat analogous use for our new chemical compound is the removal ofa residual mud sheath which remains after drilling a. well by the rotarymethod. Sometimes the drillingmud contains added calcium carbonate, orthe like, to render the mud susceptible to reaction with bydrochloricacid, or the like, and thus expedite its removal.

The new compounds herein described are of utility, not only for thepurposes specifically enumerated in detail, but also flnd application invarious other industries, processes, and for various uses where wettingagents of the conventional type are used. As to some of such additionaluses which are well known, see The expanding application of wettingagents, Chemical Industries, volume 48, page 324 (1941).

Another use for the compounds herein contemplated is in the preventionof landslides, as described in U. S. Patent No. 2,348,458, dated May 9,1944, to Endersby.

Reference is made to United States Patent No.

2,400,394, in which a process for breaking petroleum emulsions of thewater-in-oil type, using the new compounds of the present application,

76. is claimed.

wherein is the residue of the acyl radical RCO of a detergent-formingmonocarboxy acid having at least 8 and not more than 32 carbon atoms; inwhich the residue is obtained by elimination of the carbonyl oxygen atomfrom the acyl radical RCO; R1 is a member of the class consisting ofhydrogen atoms and lower alkyl radicals; R2- is a member of the classconsisting of alkylene radicals and lower alkyl substituted alkyleneradicals; X is a member of the class consisting of amino radicals andamino alkylene-substituted amino radicals, with the proviso that therebe present at least one amino radical selected from the class of primaryand secondary amino radicals; in said carbamyl compound, theaforementioned 1,2-di substituted glyoxalidine radicals being unitedthrough amino nitrogens of the radicals X by at least one memberselected from the class consisting of the radical of a higher fatty acidhaving 18 carbon atoms.

- 4. The compounds of claim 1, wherein R is the radical of-anunsaturated, higher fatty acid having 18 carbon atoms. I

5. The compounds of claim 1, wherein R is the radical of an unsaturated,higher fatty acid having 18 carbon atoms and the ratio of blyoxalidineradicals to radicals selected from the class consisting of radicalsbeing 2 to 1.

6. The compounds of claim 1, wherein R is the radical of an unsaturated,higher fatty acid having 18 carbon atoms: the ratio of glyoxalidineradicals to radicals selected from the class consisting of radicalsbeing 2 to 1, and the number of nitrogen atoms in each glyoxalidineradical being 3.

7. The compounds of claim 1, wherein R is the radical of an unsaturated,higher fatty acid having 18 carbon atoms; the ratio of glyoxalidineradicals to radicals selected from the class consisting of radicalsbeing 2 to 1, and the number of nitroen atoms in each glyoxalidineradical being 5.

MlElLVIN DE GROO'I'E. BERNHARD KEISER.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS

